Mixtures of phosphorus-containing compounds used as polymer stabilizers

ABSTRACT

The invention relates to a synergistic mixture comprising
     a) at least one compound selected from the group consisting of the phosphites of the formula (I) to (V), of the phosphonites of the formulae (VI) to (IX) and (XV), of the di/oligophosphonites of the formulae (X) and (XI) and of the phosphinites of the formulae (XII) to (XIV), and   b) at least one compound selected from the group consisting of the phosphanes of the formula (XVI), the di/oligophosphanes of the formulae (XVII) and (XVIII), and of the cyclophosphanes of the formula (XIX),
 
and also to a process for stabilizing polymers with respect to thermooxidative degradation by addition and incorporation of a synergistic mixture of this type.

The invention relates to mixtures which comprise phosphites, phosphonites, phosphinites, in particular aromatic phosphonites or phosphites (component 1) and tertiary phosphanes (component 2) and also to a process for stabilizing polymers with respect to degradation induced by heat or by mechanical stress, using mixtures of this type.

Surprisingly, it has been found that mixtures which comprise compounds of component 1 together with those of component 2 are more effective than the corresponding components alone as stabilizers for polymeric compounds.

As is known to the person skilled in the art, phosphites, phosphonites and/or phosphinites are used for stabilizing polymers with respect to thermooxidative degradation during their processing. The use of triphenylphosphane (triphenylphosphine; TPP) on its own has also been described in this connection. The stabilizing action of substances of this type is seen in that polymers stabilized in this way have substantially unchanged melt viscosity (this being a measure of constancy of molar mass) and also better color performance, i.e. a lower level of coloration after extrusion when compared with unstabilized polymers.

If mixtures of two or more additives are used, it is to be expected that properties will change linearly as a function of their mixing ratios.

However, for mixtures from the two components 1 and 2 defined above it has been found that there is an advantageous deviation from this linearity with regard to melt flow stabilization and/or color stabilization, in comparison with the linear change to be expected between the values for the individual components. This type of behavior is termed synergistic.

According to the invention, a mixture is provided comprising a component 1 as constituent (a) and a component 2 as constituent (b).

Component 1 is composed of one or more compounds of the formulae (I) to (XV):

Component 2 is one or more compounds of the general structures shown in formulae (XVI) to (XIX):

where, independently of one another,

-   R₁ is C₁–C₂₄-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₃₀-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy); -   R₂ is H, C₁–C₂₄-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₃₀-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁₀–C₁₈-alkyl (linear or     branched), C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy); -   R₃ is n-valent groups of the type C₁–C₃₀-alkylene (linear or     branched, where appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylidene (where appropriate also containing heteroatoms N,     O, P, S), C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene (where appropriate     substituted with C₁–C₁₈-alkyl (linear or branched, C₅–C₁₂-cycloalkyl     or C₁–C₁₈ alkoxy); -   R₄ is C₁–C₂₄-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₃₀-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₁₂cycloalkyl or C₁–C₁₈-alkoxy); -   R₅ is C₁–C₂₄-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₃₀-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy); -   R₆ C₁–C₂₄-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₃₀-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy); -   A is a direct bond, C₁–C₃₀-alkylidene (where appropriate also     containing heteroatoms N, O, P, S), >NH, >NR, —S—, >S(O), >S(O)₂,     —O—; -   D is q-valent groups of the type C₁–C₃₀-alkylene (linear, branched,     where appropriate also containing heteroatoms N, O, P, S),     C₁–C₃₀-alkylidene (where appropriate also containing heteroatoms N,     O, P, S), C₅–C₁₂-cycloalkylene (where appropriate also containing     heteroatoms N, O, P, S) or C₆–C₂₄-arylene (where appropriate also     substituted with C₁–C₁₈-alkyl (linear or branched, C₅–C₁₂-cycloalkyl     or C₁–C₁₈ alkoxy), —O—, —S—; -   X is Cl, Br, F, OH (including the resultant tautomeric form >P(O)H); -   k is from 0 to 4; -   n is from 1 to 4; -   m is from 0 to 5; -   p is 0 or 1; -   q is from 1 to 5; -   r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a     constituent of a phosphacycle, indicated by * on the bonds emanating     from P.

Preference is given to compounds where the radicals

-   R₁′ is C₆–C₁₂-cycloalkyl (where appropriate also containing     heteroatoms N, O, P, S), C₂–C₂₄-alkylaryl, C₆–C₂₄-aryl or     heteroaryl, C₆–C₂₄-aryl or heteroaryl (substituted with the groups     C₁–C₁₂-alkyl (linear or branched), C₅–C₈-cycloalkyl or     C₁–C₁₂-alkoxy); -   R₂′ is H, C₁–C₁₂-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₁₂-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₁₈-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₂-alkyl (linear or     branched), C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   R₃′ is n-valent groups of the type C₁–C₁₄-alkylene (linear or     branched, where appropriate also containing heteroatoms N, O, P, S),     C₁–C₁₈-alkylidene (where appropriate also containing heteroatoms N,     O, P, S), C₅–C₈-cycloalkylene or C₆–C₂₄-arylene (where appropriate     also substituted with C₁–C₁₈-alkyl (linear or branched),     C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   R₄′ is C₁–C₁₈-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₁₂-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₂₄-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   R₅′ is C₁₈–C₁₈-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₁₂-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₁₈-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   R₆′ is C₅–C₁₈-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₅–C₁₂-cycloalkyl (where     appropriate also containing heteroatoms N, O, P, S),     C₁–C₁₈-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   A′ is a direct bond, C₁–C₁₈-alkylidene (where appropriate also     containing heteroatoms N, O, P, S), >NH, —S—, —O—; -   D′ is q′-valent groups of the type C₁–C₂₄-alkylene (linear,     branched, where appropriate also containing heteroatoms N, O, P, S),     C₁–C₂₄-alkylidene (where appropriate also containing heteroatoms N,     O, P, S), C₅–C₈-cycloalkylene (where appropriate also containing     heteroatoms N, O, P, S) or C₆–C₂₄-arylene (where appropriate also     substituted with C₁–C₁₈-alkyl (linear or branched), C₅–C₈-cycloalkyl     or C₁–C₁₂-alkoxy); -   X′ is F or OH (including the resultant tautomeric form >P(O)H); -   k′ is from 0 to 3; -   n′ is from 1 to 4; -   m′ is from 0 to 3; -   p′ is 0 or 1; -   q′ is from 1 to 4; -   r′ is 4 or 5, where the groups P—R₆ in the formula (XIX) are a     constituent of a phosphacycle, indicated by * on the bonds emanating     from P.

Particular preference is given to compounds where the radicals,

-   R₁″ is C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl     (substituted with the groups C₁–C₁₂-alkyl (linear or branched),     C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   R₂″ is C₁–C₈-alkyl (linear or branched), C₅–C₈-cycloalkyl,     C₁–C₁₈-alkylaryl, C₆–C₁₂-aryl or heteroaryl, C₆–C₁₂-aryl or     heteroaryl (substituted with the groups C₁–C₁₂-alkyl (linear or     branched), C₆–C₈-cycloalkyl or C₁–C₈-alkoxy); -   R₃″ is n-valent groups of the type C₁–C₁₂-alkylene (linear or     branched where appropriate also containing heteroatoms N or P),     C₁–C₁₂-alkylidene (where appropriate also containing heteroatoms N     or P), C₆–C₈-cycloalkylene, or C₆–C₁₂-arylene (where appropriate     also substituted with C₁–C₁₂-alkyl (linear or branched),     C₆–C₈-cycloalkyl or C₁–C₈-alkoxy); -   R₄″ is C₁–C₈-alkyl (linear or branched), C₅–C₈-cycloalkyl,     C₁–C₁₈-alkylaryl, C₆–C₁₂-aryl or heteroaryl, C₆–C₁₂-aryl or     heteroaryl (substituted with the groups C₁–C₁₂-alkyl (linear or     branched), C₆–C₈-cycloalkyl or C₁–C₈-alkoxy); -   R₅″ is C₁₂–C₁₈-alkyl (linear or branched, where appropriate also     containing heteroatoms N, O, P, S), C₆–C₈-cycloalkyl,     C₁–C₁₂-alkylaryl, C₆–C₁₈-aryl or heteroaryl, C₆–C₁₈-aryl or     heteroaryl (substituted with the groups C₁–C₈-alkyl (linear or     branched), C₆–C₈-cycloalkyl or C₁–C₈-alkoxy); -   R₆″ is C₅–C₁₂-alkyl (linear or branched), C₅–C₈-cycloalkyl,     C₁–C₁₂-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or     heteroaryl (substituted with the groups C₁–C₁₈-alkyl (linear or     branched), C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy); -   A″ is a direct bond, C₁–C₁₈-alkylidene (where appropriate also     containing heteroatoms N, O, P, S), >NH, —S—, —O—; -   D″ is q″-valent groups of the type C₁–C₂₄-alkylene (linear,     branched, where appropriate also containing heteroatoms N, O, P, S),     C₁–C₂₄-alkylidene (where appropriate also containing heteroatoms N,     O, P, S), C₅–C₈-cycloalkylene (where appropriate also containing     heteroatoms N, O, P, S), or C₆–C₂₄-arylene (where appropriate also     substituted with C₁–C₁₈-alkyl (linear or branched), C₅–C₈-cycloalkyl     or C₁–C₁₂-alkoxy); -   X″ is F or OH (including the resultant tautomeric form >P(O)H); -   k″ is from 0 to 3; -   n″ is from 1 to 4; -   m″ is from 0 to 3; -   p″ is 0 or 1; -   q″ is from 1 to 4; -   r″ is 4 or 5, where the groups P—R₆ in the formula (XIX) are a     constituent of a phosphacycle indicated by * on the bonds emanating     from P.

Particularly suitable mixtures are all of those which can be formed by combining the components 1 and 2 specified below:

Component 1

-   compound mixtures whose main component is     tetrakis(di-tert-butylphenyl) biphenylyl-diphosphonite, -   tris(2,4-di-tert-butylphenyl) phosphite -   bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite -   bis(2,4-(1,1-dimethylbenzyl)phenyl) pentaerythrityl diphosphite -   bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl diphosphite -   bis(octadecyl) pentaerythrityl diphosphite -   tris(nonylphenyl) phosphite -   2,2′,2″-nitrilotriethyl     tris(3,3′-5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl phosphite) -   bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite -   2-(2,4,6-tri-tert-butylphenoxy)-5-butyl-5-ethyl-1,3,2-dioxaphosphorinane -   methylene-2,2′-bis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite -   1,1-ethylidene-2,2′-bis(4,6-di-tert-butylphenyl) fluorophosphite     Component 2 -   triphenylphosphane -   tris(2 methylphenyl)phosphane -   tris(4 methylphenyl)phosphane -   tris(2 methoxyphenyl)phosphane -   tris(4 methoxyphenyl)phosphane -   tetracyclohexyl cyclotetraphosphane -   tetratert-butyl cyclotetraphosphane -   tetrabiphenylyl cyclotetraphosphane -   tetraphenyl cyclotetraphosphane -   pentaphenyl cyclopentaphosphane -   tetraphenyl diphosphane -   tetracyclohexyl diphosphane -   bis(diphenylphosphino)methane -   1,2-bis(diphenylphosphino)ethane -   1,3-bis(diphenylphosphino)propane -   1,4-bis(diphenylphosphino)butane -   1,5-bis(diphenylphosphino)pentane -   1,6-bis(diphenylphosphino)hexane -   1,8-bis(diphenylphosphino)octane -   1,3-bis(diphenylphosphino)-2,2-dimethylpropane -   1,1,1-tris(diphenylphosphinomethyl)methane -   1,1,1-tris(diphenylphosphinomethyl)ethane -   1,1,1-tris(diphenylphosphinomethyl)propane -   1,1,1-tris(diphenylphosphinomethyl)butane -   1,1,1-tris(diphenylphosphinomethyl)-1-phenylmethane -   1,3-bis(diphenylphosphinomethyl)-2-diphenylphosphinopropane -   1,3-bis(diphenylphosphino)-2-methylpropane

Of these mixtures, any particular preference is given to the following mixtures of components 1 and 2:

-   A) where component 1 is tris(2,4-di-tert-butylphenyl) phosphite and     component 2 is tri-phenylphosphane; -   B) where component 1 is bis(2,4-di-tert-butylphenyl) pentaerythrityl     diphosphite and component 2 is triphenylphosphane; -   C) where component 1 is a mixture composed of     tetrakis(di-tert-butylphenyl) biphenylyldiphosphonite,     bis(2,4-di-tert-butylphenyl) biphenylmonophosphonite and     tris(2,4-di-tert-butylphenyl) phosphite (referred to hereinafter as     PS-1) and component 2 is triphenylphosphane; -   D) where component 1 is tris(nonylphenyl) phosphite and component 2     is triphenylphosphane; -   E) where component 1 is     2-(2,4,6-tri-tert-butylphenoxy)-5-butyl-5-ethyl-1,3,2-dioxaphos-phorinane     and component 2 is triphenylphosphane; -   F) where component 1 is tris(2,4-di-tert-butylphenyl) phosphite and     component 2 is 1,3-bis(diphenylphosphino)-2,2-dimethylpropane; -   G) where component 1 is bis(2,4-di-tert-butylphenyl) pentaerythrityl     diphosphite and component 2 is     1,3-bis(diphenylphosphino)-2,2-dimethylpropane; -   H) where component 1 encompasses the compounds of mixture PS-1 and     component 2 is 1,3-bis(diphenylphosphino)-2,2-dimethylpropane; -   I) where component 1 is tris(nonylphenyl) phosphite and component 2     is 1,3-bis-(diphenylphosphino)-2,2-dimethylpropane; -   J) where component 1 is     2-(2,4,6-tri-tert-butylphenoxy)-5-butyl-5-ethyl-1,3,2-dioxaphos-phorinane     and component 2 is 1,3-bis(diphenylphosphino)-2,2-dimethylpropane; -   K) where component 1 is tris(2,4-di-tert-butylphenyl) phosphite and     component 2 is 1,1,1-tris(diphenylphosphinomethyl)ethane; -   L) where component 1 is bis(2,4-di-tert-butylphenyl) pentaerythrityl     diphosphite and component 2 is     1,1,1-tris(diphenylphosphinomethyl)ethane; -   M) where component 1 encompasses the compounds of mixture PS-1 and     component 2 is 1,1,1-tris(diphenylphosphinomethyl)ethane; -   N) where component 1 is tris(nonylphenyl) phosphite and component 2     is 1,1,1-tris(di-phenylphosphinomethyl)ethane; -   O) where component 1 is     2-(2,4,6-tri-tert-butylphenoxy)-5-butyl-5-ethyl-1,3,2-dioxaphos-phorinane     and component 2 is 1,1,1-tris(diphenylphosphinomethyl)ethane; -   P) where component 1 is tris(2,4-di-tert-butylphenyl) phosphite and     component 2 is 1,1,1-tris(diphenylphosphinomethyl)propane; -   Q) where component 1 is bis(2,4-di-tert-butylphenyl) pentaerythrityl     diphosphite and component 2 is     1,1,1-tris(diphenylphosphinomethyl)propane; -   R) where component 1 encompasses the compounds of mixture PS-1 and     component 2 is 1,1,1-tris(diphenylphosphinomethyl)propane; -   S) where component 1 is tris(nonylphenyl) phosphite and component 2     is 1,1,1-tris(di-phenylphosphinomethyl)propane; -   T) where component 1 is     2-(2,4,6-tri-tert-butylphenoxy)-5-butyl-5-ethyl-1,3,2-dioxaphos-phorinane     and component 2 is 1,1,1-tris(diphenylphosphinomethyl)propane.

The amount of component 1 present in the mixtures of the invention is from 1 to 99% by weight, and that of component 2 is from 99 to 1% by weight.

Preferred amounts of component 1 are from 5 to 95% by weight, particularly preferably from 10 to 90% by weight, and preferred amounts of component 2 are from 95 to 5% by weight, particularly preferably from 90 to 10% by weight.

The concentration used of the mixture of the invention varies with the nature of the polymer. The person skilled in the art can readily establish the amount suitable for any given case, but typical amounts, based on the polymeric material to be stabilized, are from 0.001 to 5% by weight, preferably from 0.005 to 3% by weight, particularly preferably from 0.01 to 2% by weight.

The mixtures made from components 1 and 2 may be prepared by simple mixing, by mixing in the melt, by dissolving or dispersing one component in the liquid or molten other component, by mixing two melts, or by joint melting, in each case followed, if required, by a cooling step. Mixtures of the invention are also obtained by mixing and concentrating solutions of the components in suitable solvents. The preparation of the mixtures may either be a batch process in suitable apparatus, such as a variety of mixers or reactors, etc., or else continuous, e.g. in extruders or continuous mixers or kneaders or on roll mills. Compacting, pelletization, pressing, extruding, or some other method, may then be used to produce a suitable commercial form, if this is needed.

The invention also provides a process for stabilizing polymeric materials with respect to thermooxidative degradation. This process encompasses the addition and incorporation of a stabilizing amount of the mixture of the invention in solid or molten form, in solution (preferably as liquid concentrate) or as a solid masterbatch (if useful) prior to, during or (usually) after the polymerization stage, in amounts such that the stabilizer concentration achieved is from 0.001 to 5% by weight, preferably from 0.005 to 3% by weight, particularly preferably from 0.01 to 2% by weight, based on the polymer to be stabilized.

A liquid concentrate of this type encompasses from 10 to 80% by weight of an inventive mixture and from 90 to 20% by weight of a solvent.

A masterbatch of this type (also termed a solid base-compound) encompasses from 10 to 80% by weight, preferably from 40 to 70% by weight, particularly preferably from 15 to 40% by weight, of a mixture of the invention, and from 90 to 20% by weight, preferably from 60 to 30% by weight particularly preferably from 85 to 60% by weight, of a polymeric material which is identical or compatible with the polymeric material to be stabilized.

All of the components of the mixture of the invention may be prepared from known compounds, using known methods. An overview of reaction processes to prepare components 1 and 2 is found, for example, in G. M. Kosolapoff, Organic Phosphorus Compounds, Vols. 1–7, Wiley Verlag, New York, 1972, or in Houben/Weyl, Methoden der Organischen Chemie [Methods of organic chemistry], Vol. 12, 4th Edition, Georg Thieme Verlag, Stuttgart, 1963, and in corresponding supplementary volumes. Using this information, the person skilled in the art can prepare the compounds described above. The content of these references is incorporated herein by way of reference.

Compounds of the formula (XVIII) and compounds of the formula (XIX) are also prepared by a process which encompasses reacting either a secondary phosphane of the formula R′₁R′₁PH or a primary phosphane of the formula R′₁PH₂ with a halogen, preferably chlorine or bromine, where appropriate in the presence of an acid scavenger, such as an oxide, hydroxide or carbonate of an alkali metal or of an alkaline earth metal, or of an amine, preferably of a tertiary amine, and where appropriate in the presence of an inert solvent. Secondary phosphanes give compounds of the formula (XVIII). Primary phosphanes give compounds of the formula (XIX). In this process it is advantageous to use alkylphosphanes as starting materials, these being more readily available on a large scale than the halophosphanes used in the prior art. Examples of detailed descriptions of this process are given in FR 2739381 or GB 2306478.

Alternatively, and usually, compounds of this type are prepared from organic halides, such as alkyl or aryl chlorides, or alkyl or aryl bromides, and PCl₃, via a Grignard reaction or modified Wurtz reaction; or via a Friedel-Crafts reaction; or by an addition reaction of a P—H-containing compound onto multiple bonds, or by Arbuzov reaction of organic diphosphinites with organic halides, followed by reduction, or via derivatization of previously formed phosphanes.

The mixtures of the invention made from components 1 and 2 may be used as processing stabilizers for polymeric materials, preferably for

-   1. Polymers of monoolefins and diolefins, for example polypropylene,     polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,     polyisoprene or polybutadiene, as well as polymers of cycloolefins,     for example of cyclopentene or norbornene; furthermore polyethylene     (which optionally can be crosslinked); for example, high density     polyethylene (PE-HD), low-density polyethylene (PE-LD), linear low     density polyethylene (PE-LLD), branched low density polyethylene     (PE-BLD) Polyolefins, i.e. polymers of monoolefins, in particular     polyethylene and polypropylene, can be prepared by various, and     especially by the following, methods:     -   a) free-radical polymerization (normally under high pressure and         at elevated temperature)     -   b) catalytic polymerization using a catalyst that normally         contains one or more metals of group IVb, Vb, VIb or VIII of the         Periodic Table. These metals usually have one or more ligands,         such as oxides, halides, alcoholates, esters, ethers, amines,         alkyls, alkenyls and/or aryls that may be either π- or         σ-coordinated. These metal complexes may be in the free form or         fixed on substrates, for example on activated magnesium         chloride, titanium chloride, alumina or silicon oxide. These         catalysts may be soluble or insoluble in the polymerization         medium. The catalysts can be active as such in the         polymerization or further activators may be used, for example         metal alkyls, metal hydrides, metal alkyl halides, metal alkyl         oxides or metal alkyloxanes, the metals being elements of groups         Ia, IIa and/or IIIa of the Periodic Table. The activators may be         modified, for example, with further ester, ether, amine or silyl         ether groups. These catalyst systems are usually termed         Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),         metallocene or single site catalysts (SSC). -   2. Mixtures of the polymers mentioned under 1), e.g. mixtures of     polypropylene with polyisobutylene, polypropylene with polyethylene     (e.g. PP/HDPE, PP/LDPE) and mixtures of various grades of     polyethylene (e.g. LDPE/HDPE). -   3. Copolymers of monoolefins and diolefins with each other or with     other vinyl monomers, for example ethylene-propylene copolymers,     linear low density polyethylene (PE-LLD) and mixtures thereof with     low density polyethylene (PE-LD), propylene-but-1-ene copolymers,     propylene-isobutylene copolymers, ethylene-but-1-ene copolymers,     ethylene-hexene copolymers, ethylene-methyl-pentene copolymers,     ethylene-heptene copolymers, ethylene-octene copolymers,     propylene-butadiene copolymers, isobutylene and isoprene copolymers,     ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate     copolymers, ethylene-vinyl acetate copolymers and their copolymers     with carbon monoxide, or ethylene-acrylic acid copolymers and their     salts (ionomers) as well as terpolymers of ethylene with propylene     and a diene such as hexadiene, dicyclopentadiene or     ethylidene-norbornene; and mixtures of such copolymers with one     another and with polymers mentioned under 1), for example     polypropylene-ethylene-propylene copolymers, PE-LD-ethylene-vinyl     acetate copolymers, PE-LD-ethylene-acrylic acid copolymers,     PE-LLD-ethylene-vinyl acetate copolymers, PE-LLD-ethylene-acrylic     acid copolymers and alternating or random polyalkylene-carbon     monoxide copolymers and mixtures thereof with other polymers, for     example polyamides. -   4. Hydrocarbon resins (for example C₅–C₉) including hydrogenated     modifications thereof (e.g. tackifier resins) and mixtures of     polyalkylenes and starch. -   5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene). -   6. Copolymers of styrene or a-methylstyrene with dienes or acrylic     derivatives, for example styrene-butadiene, styrene-acrylonitrile,     styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate,     styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride,     styrene-acrylonitrile-methacrylate; mixtures of high impact strength     of styrene copolymers and another polymer, for example a     polyacrylate, a diene polymer or an ethylene-propylene-diene     terpolymer; and block copolymers of styrene, such as     styrene-butadiene-styrene, styrene-isoprene-styrene,     styrene-ethylene/butylene-styrene or     styrene-ethylene/propylene-styrene. -   7. Graft copolymers of styrene or α-methylstyrene, for example     styrene on polybutadiene, styrene on polybutadiene-styrene or     polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile     (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and     methyl methacrylate on polybutadiene; styrene and maleic anhydride     on polybutadiene; styrene, acrylonitrile and maleic anhydride or     maleimide on polybutadiene; styrene and maleimide on polybutadiene;     styrene and alkyl acrylates or alkyl methacrylates on polybutadiene,     styrene and acrylonitrile on ethylene-propylene-diene terpolymers,     styrene and acrylonitrile on polyalkyl acrylates or polyalkyl     methacrylates, styrene and acrylonitrile on acrylate-butadiene     copolymers, as well as mixtures thereof with the copolymers     mentioned under 6), for example the copolymer mixtures known as ABS,     MBS, ASA or AES polymers. -   8. Halogen-containing polymers, such as polychloroprene, chlorinated     rubber, chlorinated or sulphochlorinated polyethylene, copolymers of     ethylene and chlorinated ethylene, epichlorohydrin homo- and     copolymers, especially polymers of halogen-containing vinyl     compounds, for example polyvinyl chloride, polyvinylidene chloride,     polyvinyl fluoride, polyvinylidene fluoride; as well as copolymers     thereof such as vinyl chloride-vinylidene chloride, vinyl     chloride-vinyl acetate or vinylidene chloride-vinyl acetate. -   9. Polymers derived from α,β-unsaturated acids and derivatives     thereof, such as polyacrylates and polymethacrylates,     polyacrylonitriles, polyacrylamides and polymethyl methacrylates     impact-modified with butyl acrylate. -   10. Copolymers of the monomers mentioned under 9) with each other or     with other unsaturated monomers, for example acrylonitrile-butadiene     copolymers, acrylonitrile-alkyl acrylate copolymers,     acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl     halide copolymers or acrylonitrile-alkyl methacrylate-butadiene     terpolymers. -   11. Polymers derived from unsaturated alcohols and amines or the     acyl derivatives or acetals thereof, such as polyvinyl alcohol,     polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl     maleate, polyvinyl butyral, polyallyl phthalate or polyallyl     melamine; as well as their copolymers with olefins mentioned in     section 1. -   12. Homopolymers and copolymers of cyclic ethers, such as     polyalkylene glycols, polyethylene oxide, polypropylene oxide or     copolymers thereof with bisglycidyl ethers. -   13. Polyacetals such as polyoxymethylene and those polyoxymethylenes     which contain comonomers, for example ethylene oxide; polyacetals     modified with thermoplastic polyurethanes, acrylates or MBS. -   14. Polyphenylene oxides and sulphides, and mixtures thereof with     styrene polymers or polyamides. -   15. Polyurethanes derived from hydroxyl-terminated polyethers,     polyesters and polybutadienes on the one hand and aliphatic or     aromatic polyisocyanates on the other, as well as precursors     thereof. -   16. Polyamides and copolyamides derived from diamines and     dicarboxylic acids and/or from aminocarboxylic acids or the     corresponding lactams, such as polyamide 4, 6, 6/6, 6/10, 6/9, 6/12,     4/6, 12/12, 11 and 12, aromatic polyamides starting from m-xylene,     diamine and adipic acid; polyamides prepared from     hexamethylenediamine and isophthalic and/or terephthalic acid and     with or without an elastomer as modifier, for example     poly-2,4,4-trimethylhexamethylene terephthalamide or     poly-m-phenylene isophthalamide. Block copolymers of the     aforementioned polyamides with polyolefins, olefin copolymers,     ionomers or chemically bonded or grafted elastomers, or with     polyethers, e.g. with polyethylene glycol, polypropylene glycol or     polytetramethylene glycol. As well as polyamides or copolyamides     modified with EPDM or ABS; and polyamides condensed during     processing (RIM polyamide systems). -   17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles. -   18. Polyesters derived from dicarboxylic acids and dialcohols and/or     from hydroxycarboxylic acids or the corresponding lactones, such as     polyethylene terephthalate, polybutylene terephthalate,     poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates,     as well as block polyether-esters derived from hydroxyl-terminated     polyethers; and also polyesters modified with polycarbonates or MBS. -   19. Polycarbonates and polyester carbonates. -   20. Polysulphones, polyether sulphones and polyether ketones. -   21. Crosslinked polymers derived from aldehydes on the one hand and     phenols, urea or melamine on the other hand, such as     phenol/formaldehyde resins, urea/formaldehyde resins and     melamine/formaldehyde resins. -   22. Drying and non-drying alkyd resins. -   23. Unsaturated polyester resins derived from copolyesters of     saturated and unsaturated dicarboxylic acids with polyhydric     alcohols and vinyl compounds as crosslinking agents, and also     halogen-containing modifications thereof of low flammability. -   24. Crosslinkable acrylic resins derived from substituted acrylates,     for example from epoxy acrylates, urethane acrylates or polyester     acrylates. -   25. Alkyd resins, polyester resins and acrylic resins crosslinked     with melamine resins, urea resins, polyisocyanates or epoxy resins. -   26. Crosslinked epoxy resins which derive from polyepoxides, e.g.     from bis-glycidyl ethers or from cycloaliphatic diepoxides. -   27. Natural polymers such as cellulose, natural rubber, gelatin and     derivatives thereof which have been chemically modified in a     polymer-homologous manner, for example cellulose acetates, cellulose     propionates and cellulose butyrates, or the cellulose ethers such as     methyl cellulose; as well as rosins and derivatives. -   28. Mixtures (polyblends) of the aforementioned polymers, for     example PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,     PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,     POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,     PPO/HIPS, PPO/PA 6.6 and copolymers, PA/PE-HD, PA/PP, PA/PPO. -   29. Natural and synthetic organic substances which constitute pure     monomeric compounds or mixtures thereof, examples being mineral     oils, animal or vegetable fats, oils and waxes, or oils, waxes and     fats based on synthetic esters (e.g. phthalates, adipates,     phosphates or trimellitates), and also blends of synthetic esters     with mineral oils in any desired proportion by weight, as are     employed, for example, as spin finishes, and aqueous emulsions     thereof. -   30. Aqueous emulsions of natural or synthetic rubbers, such as     natural rubber latex or latices of carboxylated styrene-butadiene     copolymers.

Other additives may be present in these polymers, e.g. antioxidants, light stabilizers (UV absorbers and/or HALS compounds), metal deactivators, peroxide degraders, polyamide stabilizers, basic co-stabilizers, nucleating agents, fillers, reinforcing agents, plasticizers, lubricant, emulsifiers, pigments and dyes, optical brighteners, flame retardants, antistats, blowing agents, etc.

These other additives may be added to the polymers prior to, together with or after addition of the mixture of the invention. Like the mixture of the invention, these additives may be metered in as a solid, in solution or melt, or else in the form of solid or liquid mixtures or masterbatches or concentrates, either batchwise or continuously.

The invention also encompasses all of the products obtainable by way of a shaping process from the abovementioned polymers, which comprise a mixture of the invention and at least one of the other additives mentioned.

The advantageous action of the mixture prepared according to the invention is illustrated by the examples below.

EXAMPLE 1 Preparation of a Mixture of the Invention from tris(2,4-di-tert-butylphenyl) phosphite (Component 1) and triphenylphosphane (Component 2)

Pulverulent mixtures of tris(2,4-di-tert-butylphenyl) phosphite (component 1) and triphenyl-phosphane (component 2) in each of the mixing ratios given below are melted and homogenized at a temperature of 190° C., with stirring, in a 250 ml flask with stirrer having a precision glass gland, under an inert gas (N₂). The resultant melt of the mixture is poured out into a porcelain dish and hardens on cooling. The size of each batch is 100 g.

TABLE 1 Amounts of components 1 and 2 in mixtures (1) of the invention. Tris(2,4-di-tert-butyl- phenyl)phosphite Triphenylphosphane Mixture [% by weight] [% by weight] 1a 100 0 1b 70 30 1c 50 50 1d 30 70 1e 0 100

EXAMPLE 2 Preparation of a Mixture of the Invention from bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite (Component 1) and triphenylphosphane (Component 2)

Pulverulent mixtures of bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite (component 1) and triphenylphosphane (component 2) in each of the mixing ratios given below are melted and homogenized at a temperature of 190° C., with stirring, in a 250 ml flask with stirrer having a precision glass gland, under an inert gas (N₂). The resultant melt of the mixture is poured out into a porcelain dish and hardens on cooling. The size of each batch is 100 g.

TABLE 2 Amounts of components 1 and 2 in mixtures (2) of the invention. Bis(2,4-di-tert-butyl-phenyl) pentaerythrityl diphosphite Triphenylphosphane Mixture [% by weight] [% by weight] 2a 100 0 2b 70 30 2c 50 50 2d 30 70 2e 0 100

EXAMPLE 3 Preparation of a Mixture of the Invention from tetrakis(2,4-di-tert-butylphenyl) biphenylyl-diphosphonite (Main Component in the Sandostab P-EPQ, Used, CLARIANT AG) (Component 1) and triphenylphosphane (Component 2)

Pulverulent mixtures of Sandostab P-EPQ (component 1) and triphenylphosphane (component 2) in each of the mixing ratios given below are melted and homogenized at a temperature of 190° C., with stirring, in a 250 ml flask with stirrer having a precision glass gland, under an inert gas (N₂). The resultant melt of the mixture is poured out into a porcelain dish and hardens on cooling. The size of each batch is 100 g.

TABLE 3 Amounts of components 1 and 2 in the mixtures (3) of the invention. Sandostab P-EPQ Triphenylphosphane Mixture [% by weight] [% by weight] 3a 100 0 3b 70 30 3c 50 50 3d 30 70 3e 0 100

EXAMPLE 4

To prepare a polymer (4a) stabilized according to the invention,

100 parts of polypropylene (eltex P HL 001PF, Solvay) 0.05 parts of Irganox 1010 0.10 parts of calcium stearate and 0.04 parts of the mixture (1a) of the invention in powder form are mixed in a mixer and then homogenized by extrusion under mild conditions in a single-screw extruder (Collin, 210° C., 80/min, compr. 1:3, die 4 mm), and the resultant polymer extrudate is pelletized. Stabilized polymers (4b) to (4e) are prepared similarly from mixtures (1b) to (1e).

To study melt flow stabilization and color stabilization, these stabilized polymers (4a) to (4e) are subjected to 5-fold extrusion at 270° C. in a single-screw extruder (Göttfert Extrusiometer, 50/min, compr. 1:3, die 2 mm). Melt flow index (MFI) to ASTM 1238 cond. L (230° C./2.16 kg) and Yellowness Index (YI) to DIN 6167 are determined after the fifth pass. The results obtained are given in the table below.

TABLE 4 Results for melt flow stabilization and color stabilization of PP using 0.04 parts of mixtures (1a) to (1e) Triphenyl- Stabilized phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 4a 0 13.48 10.8 4b 30 9.99 9.6 4c 50 6.49 10.4 4d 70 4.63 10.3 4e 100 4.80 11.8

EXAMPLE 5

Stabilized polymers (5a) to (5e) are prepared in a manner similar to that in example 4 from mixtures (1a) to (1e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 5 Results for melt flow stabilization and color stabilization of PP using 0.07 part of mixtures (1a) to (1e) Triphenyl- Stabilized phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 5a 0 10.85 12.8 5b 30 5.60 10.2 5c 50 4.51 10.2 5d 70 4.43 8.6 5e 100 4.24 8.3

EXAMPLE 6

Stabilized polymers (6a) to (6e) are prepared in a manner similar to that in example 4 from mixtures (2a) to (2e) at a concentration of 0.04 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 6 Results for melt flow stabilization and color stabilization of PP using 0.04 part of mixtures (2a) to (2e) Triphenyl- Stabilized phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 6a 0 5.34 8.5 6b 30 4.55 5.3 6c 50 4.19 5.5 6d 70 4.75 9.9 6e 100 4.80 11.8

EXAMPLE 7

Stabilized polymers (7a) to (7e) are prepared in a manner similar to that in example 4 from mixtures (2a) to (2e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 7 Results for melt flow stabilization and color stabilization of PP using 0.07 part of mixtures (2a) to (2e) Triphenyl- Stabilized phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 7a 0 4.27 6.2 7b 30 4.09 4.3 7c 50 3.58 4.5 7d 70 3.78 5.5 7e 100 4.24 8.3

EXAMPLE 8

Stabilized polymers (8a) to (8e) are prepared in a manner similar to that in example 4 from mixtures (3a) to (3e) at a concentration of 0.04 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 8 Results for melt flow stabilization and color stabilization of PP using 0.04 part of mixtures (3a) to (3e) Triphenyl- Stabilized phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 8a 0 8.28 8.0 8b 30 6.30 8.4 8c 50 5.11 7.9 8d 70 4.70 9.4 8e 100 4.80 11.8

EXAMPLE 9

Stabilized polymers (9a) to (9e) are prepared in a manner similar to that in example 4 from mixtures (3a) to (3e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 9 Results for melt flow stabilization and color stabilization of PP using 0.07 part of mixtures (3a) to (3e) Triphenyl- Stabilized phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 9a 0 5.23 7.5 9b 30 4.43 5.9 9c 50 4.04 5.8 9d 70 4.21 6.5 9e 100 4.24 8.3

As clearly shown by the results of examples (4) to (9), all of these mixtures (1) to (3) of the invention have markedly synergistic behavior for use as stabilizers, and this is particularly readily discernible if the results are presented graphically (MFI and, respectively, YI against concentration of a component in the mixture). In all cases, the curve for the property measured (MFI value or YI value) lies well below the theoretically expected straight line connecting the individual components, i.e. the property is much better than expected in the mixture.

EXAMPLE 10 Preparation of a Mixture of the Invention from tris(2,4-di-tert-butylphenyl) phosphite (Component 1) and bis(diphenylphosphino)-2,2-dimethylpropane (Component 2)

Pulverulent mixtures of tris(2,4-di-tert-butylphenyl) phosphite (component 1) and bis(diphenylphosphino)-2,2-dimethylpropane (component 2) in each of the mixing ratios given below are melted and homogenized at a temperature of 190° C., with stirring, in a 250 ml flask with a stirrer with precision glass gland, under an inert gas (N₂). The resultant melt of the mixture is poured out into a porcelain dish, and hardens on cooling. The size of each batch is 50 g.

TABLE 10 Amounts of components 1 and 2 in mixtures (10) of the invention. Tris(2,4-di-tert-butyl- Bis(diphenylphosphino)- phenyl)phosphite 2,2-dimethylpropane Mixture [% by weight] [% by weight] 10a 100 0 10b 70 30 10c 50 50 10d 30 70 10e 0 100

EXAMPLE 11 Preparation of a Mixture of the Invention from tris(2,4-di-tert-butylphenyl) phosphite (Component 1) and 1,1,1-tris(diphenylphosphinomethyl)propane (Component 2)

Pulverulent mixtures of tris(2,4-di-tert-butylphenyl)phosphite (component 1) and 1,1,1-bis(diphenylphoshinomethyl)propane (component 2) in each of the mixing ratios given below are melted and homogenized at a temperature of 190° C., with stirring, in a 250 ml flask with a stirrer with precision glass gland, under an inert gas (N₂). The resultant melt of the mixture is poured out into a porcelain dish, and hardens on cooling. The size of each batch is 50 g.

TABLE 11 Amounts of components 1 and 2 in mixtures (11) of the invention. 1,1,1-Tris- Tris(2,4-di-tert-butyl- (diphenylphosphino- phenyl)phosphite methyl)propane Mixture [% by weight] [% by weight] 11a 100 0 11b 70 30 11c 50 50 11d 30 70 11e 0 100

EXAMPLE 12

To prepare a polymer (12a) stabilized according to the invention,

100.00 parts of Linear low-density polyethylene (LLDPE) 0.05 part of Hostanox O 16 0.10 part of Calcium stearate and 0.04 part of the mixture (10a) of the invention are mixed in powder form in a mixer and then homogenized by extrusion under mild conditions in a single-screw extruder (Haendle, KPS 25, 210° C., 80/min, compr. 1:3, die 4 mm), and the resultant polymer extrudate is pelletized. Stabilized polymers (12b) to (12e) are prepared similarly from mixtures (10b) to (10e).

To study melt flow stabilization and color stabilization, these stabilized polymers (12a) to (12e) are subjected to 5-fold extrusion at 240° C. in a single-screw extruder (Göttfert Extrusiometer, 70/min, compr. 1:3, die 4 mm). Melt flow index (MFI) to ASTM 1238 cond. L (190° C./2.16 kg) and Yellowness Index (YI) to DIN 6167 are determined after the fifth pass. The results obtained are given in the table below.

TABLE 12 Results for melt flow stabilization and color stabilization LLDPE using 0.04 part of mixtures (10a) to (10e) Bis(diphenyl-phosphino)-2,2- Stabilized dimethylpropane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 12a 0 1.35 10.51 12b 30 1.60 9.88 12c 50 1.83 9.13 12d 70 2.08 8.16 12e 100 2.19 8.41

EXAMPLE 13

Stabilized polymers (13a) to (13e) are prepared in a manner similar to that in example 12 from mixtures (10a) to (10e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 13 Results for melt flow stabilization and color stabilization LLDPE using 0.07 part of mixtures (10a) to (10e) Bis(diphenyl-phosphino)-2,2- Stabilized dimethylpropane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 13a 0 1.51 9.58 13b 30 1.87 7.00 13c 50 2.11 7.34 13d 70 2.25 5.69 13e 100 2.28 4.25

EXAMPLE 14

Stabilized polymers (14a) to (14e) are prepared in a manner similar to that in example 12 from mixtures (11a) to (11e) at a concentration of 0.04 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 14 Results for melt flow stabilization and color stabilization LLDPE using 0.04 part of mixtures (11a) to (11e) 1,1,1-Tris(diphenyl- Stabilized phosphinomethyl)-propane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 14a 0 1.35 10.51 14b 30 1.65 6.20 14c 50 1.85 5.00 14d 70 1.99 5.41 14e 100 2.13 9.12

EXAMPLE 15

Stabilized polymers (15a) to (15e) are prepared in a manner similar to that in example 12 from mixtures (11a) to (11e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 15 Results for melt flow stabilization and color stabilization LLDPE using 0.07 part of mixtures (15a) to (15e) 1,1,1-Tris(diphenyl- Stabilized phosphinomethyl)-propane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 15a 0 1.51 9.58 15b 30 1.96 5.49 15c 50 2.07 5.40 15d 70 2.21 3.67 15e 100 2.27 4.40

EXAMPLE 16

Stabilized polymers (16a) to (16e) are prepared in a manner similar to that in example 12 from mixtures (1a) to (1e) at a concentration of 0.04 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 16 Results for melt flow stabilization and color stabilization LLDPE using 0.04 part of mixtures (1a) to (1e) Stabilized Triphenyl-phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 16a 0 1.35 10.51 16b 30 1.71 7.63 16c 50 1.95 6.83 16d 70 1.96 8.64 16e 100 2.15 11.55

EXAMPLE 17

Stabilized polymers (17a) to (17e) are prepared in a manner similar to that in example 12 from mixtures (1a) to (1e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 17 Results for melt flow stabilization and color stabilization LLDPE using 0.07 part of mixtures (1a) to (1e) Stabilized Triphenylphosphane 5th Pass Polymers [% by weight] MFI [g/10 min] 17a 0 1.51 17b 30 2.02 17c 50 2.04 17d 70 2.16 17e 100 2.30

EXAMPLE 18

To prepare a polymer (18a) stabilized according to the invention,

100.00 parts of High-density polyethylene (HDPE) 0.05 parts of Hostanox O 10 0.10 parts of Calcium stearate and 0.04 parts of the mixture (10a) of the invention are mixed in powder form in a mixer and then homogenized by extrusion under mild conditions in a single-screw extruder (Haendle, KPS 25, 210° C., 80/min, compr. 1:3, die 4 mm), and the resultant polymer extrudate is pelletized. Stabilized polymers (18b) to (18e) are prepared similarly from mixtures (10b) to (10e).

To study melt flow stabilization and color stabilization, these stabilized polymers (18a) to (18e) are subjected to 5-fold extrusion at 240° C. in a single-screw extruder (Göttfert Extrusiometer, 70/min, compr. 1:3, die 3 mm). Melt flow index (MFI) to ASTM 1238 cond. L (190° C./2. 16 kg) and Yellowness Index (YI) to DIN 6167 are determined after the fifth pass. The results obtained are given in the table below.

TABLE 18 Results for melt flow stabilization and color stabilization HDPE using 0.04 part of mixtures (10a) to (10e) Bis(diphenyl-phosphino)-2, Stabilized 2-dimethylpropane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 18a 0 6.15 2.92 18b 30 7.00 1.06 18c 50 6.92 −0.95 18d 70 6.87 −1.19 18e 100 6.84 −1.00

EXAMPLE 19

Stabilized polymers (19a) to (19e) are prepared in a manner similar to that in example 18 from mixtures (10a) to (10e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 19 Results for melt flow stabilization and color stabilization HDPE using 0.07 part of mixtures (10a) to (10e) Bis(diphenyl-phosphino)-2, Stabilized 2-dimethylpropane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 19a 0 6.46 2.73 19b 30 6.64 −1.98 19c 50 6.84 −1.40 19d 70 6.61 −1.85 19e 100 6.70 −1.08

EXAMPLE 20

Stabilized polymers (20a) to (20e) are prepared in a manner similar to that in example 18 from mixtures (11a) to (11e) at a concentration of 0.04 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 20 Results for melt flow stabilization and color stabilization HDPE using 0.04 part of mixtures (11a) to (11e) 1,1,1-Tris(diphenyl- Stabilized phosphinomethyl)-propane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 20a 0 6.15 2.92 20b 30 6.89 2.67 20c 50 6.84 2.10 20d 70 6.61 −0.48 20e 100 6.82 −1.36

EXAMPLE 21

Stabilized polymers (21a) to (21e) are prepared in a manner similar to that in example 18 from mixtures (11a) to (11e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 21 Results for melt flow stabilization and color stabilization HDPE using 0.07 part of mixtures (11a) to (11e) 1,1,1-Tris(diphenyl- Stabilized phosphinomethyl)-propane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 21a 0 6.46 2.73 21b 30 6.90 1.44 21c 50 6.87 0.19 21d 70 6.92 −0.48 21e 100 6.84 −0.25

EXAMPLE 22

Stabilized polymers (22a) to (22e) are prepared in a manner similar to that in example 18 from mixtures (1a) to (1e) at a concentration of 0.04 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 22 Results for melt flow stabilization and color stabilization HDPE using 0.04 part of mixtures (1a) to (1e) Stabilized Triphenyl-phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 22a 0 6.15 2.92 22b 30 6.89 0.96 22c 50 6.74 1.69 22d 70 7.00 −0.92 22e 100 6.59 0.04

EXAMPLE 23

Stabilized polymers (23a) to (23e) are prepared in a manner similar to that in example 18 from mixtures (1a) to (1e) at a concentration of 0.07 part of the mixtures of the invention, and are tested correspondingly. The results are given in the table below.

TABLE 23 Results for melt flow stabilization and color stabilization HDPE using 0.07 part of mixtures (1a) to (1e) Stabilized Triphenyl-phosphane 5th Pass Polymers [% by weight] MFI [g/10 min] YI 23a 0 6.46 2.73 23b 30 6.88 −0.35 23c 50 6.91 −0.64 23d 70 6.86 −1.26 23e 100 6.85 −0.04

As clearly shown by the results of these examples, these mixtures (1) to (3), and also (10) and (11), of the invention have markedly synergistic behavior for use as stabilizers, and this is particularly readily discernible if the results are presented graphically (MFI and, respectively, YI against concentration of a component in the mixture). In all cases, the curve for the property measured (MFI value or YI value) lies on the side of better stabilization and therefore below (MFI of PP and all of the YI) or above (MFI of LLDPE and HDPE) the theoretically to be expected straight line connecting the individual components, i.e. the property is better in the mixture than would be expected from linear interpolation. 

1. A stabilized polymer comprising at least one polymer, wherein the at least one polymer is selected from the group consisting of polyolefins and polyesters; and at least one stabilizer mixture, wherein the at least one stabilizer mixture comprises a) at least one compound selected from the group of compounds of the formulae (I) to (IX) and (XI) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVII) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy, R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P.
 2. A stabilized polymer according to claim 1, where, independently of one another R₁ is C₆–C₁₂-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₂–C₂₄-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₂-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; R₂ is H, C₁–C₁₂-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₁₈-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₂-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; R₃ is an n-valent group C₁–C₁₄-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₁₈-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₈-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂ alkoxy R₄ is C₁–C₁₈-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₂₄-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; R₅ is C₈–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₁₈-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₅–C₁₈-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₁₈-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; A is a direct bond, C₁–C₁₈-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, —S—, —O—; D is q-valent group C₁–C₂₄-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₂₄-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₈-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; X is F or OH including the resultant tautomeric form >P(O)H; k is from 0 to 3; n is from 1 to 4; m is from 0 to 3; p is 0 or 1; q is from 1 to 4; r is 4 or 5, where the groups P—R₆ in the formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P.
 3. A stabilized polymer according to claim 1, where, independently of one another, R₁ is C₆–C₂₄-aryl or heteroaryl, or C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₂-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; R₂ is C₁–C₈-alkyl linear or branched, C₅–C₈-cycloalkyl, C₁–C₁₈-alkylaryl, C₆–C₁₂-aryl heteroaryl, C₆–C₁₂-aryl or heteroaryl substituted with the groups C₁–C₁₂-alkyl linear or branched, C₆–C₈-cycloalkyl or C₁–C₈-alkoxy; R₃ is an n-valent group C₁–C₁₂-alkylene linear or branched optionally containing heteroatoms N or P, C₁–C₁₂-alkylidene optionally containing heteroatoms N or P, C₆–C₈-cycloalkylene, or C₆–C₁₂-arylene optionally substituted with C₁–C₁₂-alkyl linear or branched, C₆–C₈-cycloalkyl or C₁–C₈-alkoxy; R₄ is C₁–C₈-alkyl linear or branched, C₅–C₈-cycloalkyl, C₁–C₁₈-alkylaryl, C₆–C₁₂-aryl or heteroaryl, C₆–C₁₂-aryl or heteroaryl substituted with the groups C₁–C₁₂-alkyl linear or branched, C₆–C₈-cycloalkyl or C₁–C₈-alkoxy; R₅ is C₁₂–C₁₈-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₆–C₈-cycloalkyl, C₁–C₁₂-alkylaryl, C₆–C₁₈-aryl or heteroaryl, C₆–C₁₈-aryl or heteroaryl substituted with the groups C₁–C₈-alkyl linear or branched, C₆–C₈-cycloalkyl or C₁–C₈-alkoxy; R₆ is C₅–C₁₂-alkyl linear or branched, C₅–C₈-cycloalkyl, C₁–C₁₂-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; A is a direct bond, C₁–C₁₈-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, —S—, or —O—; D is q-valent group C₁–C₂₄-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₂₄-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₈-cycloalkylene optionally containing heteroatoms N, O, P, or S, or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₈-cycloalkyl or C₁–C₁₂-alkoxy; X is F or OH including the resultant tautomeric form >P(O)H; k is from 0 to 3; n is from 1 to 4; m is from 0 to 3; p is 0 or 1; q is from 1 to 4; r is 4 or 5, where the groups P—R₆ in the formula (XIX) are a constituent of a phosphacycle indicated by * on the bonds emanating from P.
 4. A stabilized polymer according to claim 1, where the proportion by weight of the at least one first compound is from 1 to 99% by weight, and the proportion by weight of the at least one second compound is from 99 to 1% by weight.
 5. A process for stabilizing a polymer with respect to thermooxidative degradation, comprising the step of adding a stabilizing mixture to a polymer, wherein the polymer is selected from the group consisting of polyolefins and polyesters, wherein the stabilizing mixture is added in an amount of from 0.001 to 5% by weight based on the polymer and wherein the stabilizing mixture comprises a) at least one first compound selected from the group of compounds of the formulae (I) to (IX) and (XI) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVII) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy; R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P.
 6. A stabilized polymer comprising at least one polymer and at least one stabilizer mixture, wherein the at least one stabilizer mixture comprises: a) at least one first compound selected from the group of compounds of the formulae (I) to (IX) and (XI) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVII) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy; R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, or —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P, wherein the proportion by weight of the at least one first compound is from 5 to 95% by weight, and the proportion by weight of the at least one second compound is from 95 to 5% by weight.
 7. A stabilized polymer comprising at least one polymer and at least one stabilizer mixture, wherein the at least one stabilizer mixture comprises: a) at least one first compound selected from the group of compounds of the formulae (I) to (IX) and (XI) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVII) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy; R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P, wherein the proportion by weight of the at least one first compound is from 10 to 90% by weight, and the proportion by weight of the at least one second compound is from 90 to 10% by weight.
 8. The process of claim 5, wherein the stabilizing mixture is in the form selected from the group consisting of solid, liquid/molten, in solution, and a solid masterbatch.
 9. The process of claim 5, wherein the stabilizing mixture is added in the amount of from 0.005 to 3% by weight, based on the polymer.
 10. The process of claim 5, wherein the stabilizing mixture is added in the amount of from 0.01 to 2% by weight, based on the polymer.
 11. A polymer made in accordance with the process of claim
 5. 12. A stabilized polymer comprising at least one polymer selected from the group consisting of polyolefins and polyesters; and at least one stabilizer mixture, wherein the at least one stabilizer mixture comprises a) at least one first compound selected from the group of compounds of the formulae (I) to (IX) and (XI) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVI) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy; R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P.
 13. A stabilized polymer comprising at least one polymer selected from the group consisting of polyolefins and polyesters; and at least one stabilizer mixture, wherein the at least one stabilizer mixture comprises a) at least one first compound selected from the group of compounds of the formulae (I) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVII) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy; R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P.
 14. A masterbatch composition comprising from 90 to 20% by weight of at least one polymer selected from the group (1) to (14) and (16) to (29), wherein group (1) is polymers of mono olefins or diolefins, (2) is mixtures of polymers of monoolefins and diolefins, (3) is copolymers of monoolefins and diolefins, (4) is hydrocarbon resins, (5) is polystyrenes, (6) is copolymers of styrene or alpha-methylstyrene with dienes or acrlic derivatives, (7) is graft copolymers of styrene or alpha-methylstyrene, (8) is halogen-containing polymers, (9) is polymers derived from alpha,beta-unsaturated acids and derivatives thereof, (10) is copolymers of alpha,beta-unsaturated acids and derivatives thereof with each other or with other unsaturated monomers, (11) is polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof; or copolymers thereof with olefins, (12) is homopolymers and copolymers of cyclic ethers, or copolymers thereof with bisglycidyl ethers, (13) is polyacetals or polyoxymethylenes containing comonomers, (14) is polyphenylene oxides or sulphides, and mixtures thereof with styrene polymers or polyamides, (16) is polyamides and copolyamides, block copolymers of polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers; polyamides or copolyamides modified with EPDM or ABS; or polyamides condensed during processing, (17) is polyimides, polyamide-imides or polybenzimidazoles, (18) is polyesters, block polyether-esters derived from hydroxyl-terminated polyethers; or polyesters modified with polycarbonates or MBS, (19) is polycarbonates or polyester carbonates, (20) is polysulphones, polyether sulphones or polyether ketones, (21) is crosslinked polymers derived from aldehydes phenols, urea or melamine, (22) is drying or non-drying alkyd resins, (23) is unsaturated polyester resins or halogen-containing modifications thereof, (24) is crosslinkable acrylic resins derived from substituted acrylates, (25) is alkyd resins, polyester resins or acrylic resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins, (26) is crosslinked epoxy resins derived from polyepoxides, (27) is cellulose, natural rubber, gelatin and derivatives thereof which have been chemically modified in a polymer-homologous manner, cellulose ethers rosins and derivatives thereof, (28) is mixtures of the polymers of groups (1) to (14) and (15) to (27), and (29) is pure monomeric natural and synthetic organic substances or mixtures thereof, and from 10 to 80% by weight of at least one stabilizer mixture, wherein the at least one stabilizer mixture comprises a) at least one first compound selected from the group of compounds of the formulae (I) to (XV)

 and b) at least one second compound selected from the group consisting of compounds of the formulae (XVI) to (XIX)

 where, independently of one another, each group R₁ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₂ is H, C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₃ is an n-valent group C₁–C₃₀-alkylene linear or branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈ alkoxy; R₄ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₅ is C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or S, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; R₆ C₁–C₂₄-alkyl linear or branched, optionally containing heteroatoms N, O, P, or, C₅–C₃₀-cycloalkyl optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylaryl, C₆–C₂₄-aryl or heteroaryl, C₆–C₂₄-aryl or heteroaryl substituted with the groups C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl or C₁–C₁₈-alkoxy; A is a direct bond, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, >NH, >NR₁, —S—, >S(O), >S(O)₂, —O—; D is a q-valent group C₁–C₃₀-alkylene linear, branched, optionally containing heteroatoms N, O, P, or S, C₁–C₃₀-alkylidene optionally containing heteroatoms N, O, P, or S, C₅–C₁₂-cycloalkylene optionally containing heteroatoms N, O, P, or S or C₆–C₂₄-arylene optionally substituted with C₁–C₁₈-alkyl linear or branched, C₅–C₁₂-cycloalkyl C₁–C₁₈ alkoxy, —O—, —S—; X is Cl, Br, F, OH including the resultant tautomeric form >P(O)H; k is from 0 to 4; n is from 1 to 4; m is from 0 to 5; p is 0 or 1; q is from 1 to 5; r is from 3 to 6, where the groups P—R₆ in formula (XIX) are a constituent of a phosphacycle, indicated by * on the bonds emanating from P.
 15. A masterbatch composition according to claim 14, wherein the proportion by weight in the stabilizer mixture of the at least one first compound is from 1 to 99% by weight, and the proportion by weight of the at least one second compound is from 99 to 1% by weight.
 16. A masterbatch composition according to claim 14, wherein the proportion by weight in the stabilizer mixture of the at least one first compound is from 5 to 95% by weight, and the proportion by weight of the at least one second compound is from 95 to 5% by weight.
 17. A masterbatch composition according to claim 14, wherein the proportion by weight in the stabilizer mixture of the at least one first compound is from 10 to 90% by weight, and the proportion by weight of the at least one second compound is from 90 to 10% by weight. 